Process for separating predomi



Oct. 13, 1953 H B H. COOPER EI'AL 2,655,457 PROCESS FOR SEPARATING PREDOMINANTLY AROMATIC aymaocmsous mom PREDOMINANTLY SATURATED 4 ayoaocmsons BY EXTRACTIVE DISTILLATION Filed am 27, 1952 5 Shuts-Sheet 1 INVENTORS ATTORNEY 1953 H. B. H. COOPER EIAL 2,655,467

PROCESS SEPARATING PREDOMINANTLY AROMATIC HYDROC ONS M PREDOMINANTLY SATURATED HYDROCARBONS EXTRACTIVE DISTILLATION Filed May 27, 1952 5 Sheets-Sheet 2 Oct. 13, 1953' H. B. H ROCESS FOR SEPARATING PREDOMINANTLY AROMATIC HYDROCARBONS FROM PREDOMINANTLY SATURATED HYDROCARBONS BY EXTRACTIVE DISTILLATION Filed May 27, 1952 5 Sheets-Sheet 3 COOPER EI'AL ,4 7

INVENTORS HAM 6. A. COOPER Oct. 13,1953 H. B. H. co ER HAL 2,655,467

HYDROCARBONS FROM PREDOMINANTLY SATURATED HYDROCARBONS BY EXTRACTIVE DISTILLATION Oct. 13, 1953 ATTORNEY Patented Oct. 13, 1953 OFFICE ROCARBON S FROM PREDOMINANTLY SATURATED YDROCARB NS Y DISTILLATION Hal B. H. Cooper and Eugene Brook, N. J Company, New York, N. Y Maine Application May 27, 1952, Serial N 0.

EXTRACTIVE C. Medcalf, Bound assignors to American Cyanamid a corporation of 10 Claims. (01. 20239.5)

to an improved process for separating. predominantly aromatic compounds, such as naphthalene, from predominantby m ans of extractive distillation. More particularly, the process lates to the treatment of mixtures obtained in petroleum refining or processing which contain both and. predominantly saturated constituents which boil so close to the same temperature that separation by ordinary means is not feasible.

In recent years many of the products obtained from various cracking processes in petroleum refining contain considerable quantities of arcmatic hydrocarbons, such as naphthalene. Typi licht cvcle naphthalene may main, three types of constituents. The bulk of the product is such as dodec- There is a considerable portion of napha considerable problem. In the first place, the presence of these reduces the value of the paraffin for certain fuels, for example, fuels for jet engines; and the aromatics, such naphthalene, t price and constitute a considerused in the synthetic Separation of are-- c, distillation is not satisfactory because the boiling points are too near, and formation of azeotro oes renders a sharp on a commercial scale.

been removed by solvent proc also been used processes ins-o-called extractive distillation in which an additional compound is added which changes the relative va or pre. sures of stituents of the deals.

course, to use present serious corrosion Among the tion, in the solvents used in extractiv distillapast, has been dimethyl phthalate,

gas 011 However, the ester leaves much to be desired In the first place, it produces only a moderate difference in Volatility of the conlost and its solubility in the predominantly satucorrosion problem. In every respect phthalic superior to the best solvents used in the past, such as dimethyl phthalate, and the technical and economic advantages are ob By preis meant hydrocarbons in such as s inewhat unsaturated as naphthalene and paraffin. hydrocarbons of.

similar boiling points. However; excellent separation may be made when the compound" is not 100% aromatic, for example, tetralin in which more than half of the weight of the molecule: is in the form of the benzenoid ring can beeffectively separated from paraflin hydrocarbons of similar boiling points. Alternatively, tetralin can be separated from the completely saturated: decalin by means of the present process. treatment of most products from the refining of petroleum, which is themost important single field for. the present invention, the mixtures are: normally heterogeneous. Thus, for example, there maybe more than one predominantly are matic compound associated with several predominantly saturatedhydrocarbons. Itis an ad'- vantage" of the process that it can be used with: crude mixtures as well as in the separation of mixtures of a single aromatic hydrocarbon with a single saturated hydrocarbon.

it is an advantage of the present invention that phthali c anhydride can easilybe removed completelywhere this is necessary because it is'pos'-- sible to take out small traces of phthal'ic' anh-y dride from either an aromatic hydrocarbon or a predominantly saturated hydrocarbon because the phthalic anhydride is soluble in aqueous caustic alkali solutions. The possibility of removing even small traces of the extractive solvent is sometimes of importance where products of the greatest purity are necessary; This advantage is a marked one over other solvents which have been used in the past such as. di methyl phthalate which present a serious problem when absolute purity of product is necessary.

The operation of the invention is simple,

phthalic anhydride being soluble-in the predominantly aromatic component and therefore lowering its vapor pressure while at the same time the partial vapor pressure of the predominantly saturated hydrocarbon is increased. A vapor pressure difierence is thus created which permits sharp separations in equipment of practical size and capacity; Fractional. distillation columns of conventional design may be used. Aspointed out above, where extreme purity is necessary,

traces of phthalic anhydride may be removed from either component by washing with caustic alkali.

rhe invention will be described in greater detail in conjunction with the drawings in which Fig. l is a diagrammatic representation of a typical plant using the present invention; and

Fig. 2 is a graph showing the increased separation of dodecane from naphthalene in the presence of phthalic anhydride and dimethyl phthalate; and

Fig. 3 is a curve showing the change in relative volatility of dodecane and naphthalene in the presence of phthalic anhydride and dimethyl phthalate; and a Fig. 4 is a graph showing the increased separation of ZA-dimethylpentane from benzene in the presence of phthalic anhydride; and r Fig. 5 is a graph showing the change in rela- 7' tive volatility of benzene and 2,4-dimethylpen- Many of the most important mixtures;

phthalic anhydrid'e as in the presence of dimethyl phthalate: Fig. 3 shows a similar effect withvariousepercentages oi dodecane and naphthalene. Thus, for instance, at 50%, which is used commonly, for comparison purposes, the increase in relative volatility of dodecane to naphthalene is; about 2 /4 times-with: dimethylphthalate, and over: three times with phthalic anhy dride'.

Figs. 4 and 5* show thatiphthalic anhydride has: a similar effect in: enhancing the separation; 01'. benzene and 2,4-diinethylpentane in a petroleum; fraction containing them and the changes: in. volatility of the two constituents which are efiected by the phthalic anhydride. For equi-= molecular mixtures, the relative volatility, when phthalic anhydride is present, is 3.5 times that: of the binary system alone;-

Fig. 6 shows that the separation of benzene and cyclohexa-ne is likewise greatly facilitated by the. presence of phthalic anhydri'de. Pressure is of course needed to maintain the reaction above the melting point of phthalic anhydride. In a sim ilar manner, Fig. '7' shows improved separation of dodecane and tetralin.

The above figures show the cheat of phthalic anhydride on the vapor-liquid equilibria of four of the many possible mixtures of a saturated by drocarbon, or mixtures of saturated hydrocar bone, with predominantly aromatic cyclic hydrocarbons, which present difficulti'es in separation by ordinary distillation. Practically any aromatic hydrocarbon oralkyl derivative thereof, such as benzene, toluene, xylene, tetralin, alphaand beta-methylnaphthalene, and similar types of predominantly aromatic compounds, give vaporliquid diagrams, when mixed with saturated hydrocarbons of similar boiling points, similar to those of the foregoing figures. The relative volatilities in the presence of hthalicanhydride vary somewhat with the particular mixtures used; but the variations are not great and the use of phthalic anhydride brings out comparable improvements in separation in each case.

The drawings have shown two component mixtures in order togive accurately reproduciblefigures. It should be understood that in commercial practice perfect two-component mixtures are seldom encountered; however, the behavior of multicomponent mixtures, where several saturated hydrocarbons and predominantly aromatic hydrocarbons of similar boiling ranges are encountered, show the same general behavior with phthalic anhydride, thus permitting the improvements of the present invention to be obtained in the practical separation of many petroleum fractions, which hitherto have been most dinicult to separate. Of course, when a polycomponent mix ture is treated, pure compounds will not be produced. In other words, if there are two or more saturated hydrocarbons of comparable boiling point present in the mixture, they will be rereflux accumulator 22. A portion of the liquid covered together; and the same applies to the from the latter is introduced through the pipe 23 aromatic hydrocarbons. into the top of the solvent recovery still 15, the A typical extractive distillation process will be bulk passing through the pipe 24 to storage. described in connection with Fig. 1. In this fig- This application is in part a continuation of symbolized on the diagrammatic drawing of Fig. We claim: 1 by the letters A, N, and P, is introduced into a 1. A pro typical extractive distillation still I, at a point matic hydrocarbons from predominantly satu- The solvent, phthalic anhydride, symbolized on weight in benzenoid rings and hydrocarbons of and reducing the vapor pressure of the aromatics 2O 0 a. stream of molten phthalic anhydride wherein olution th aro tic nantly saturated hydrocarbons being obtained as The upper portion of th olu 2 above t an overhead and a solution of phthalic anhydride solvent inlet 9 ized phthalic anhydride is condensed and flows A proeees 9 ding to claim 1 111 which the down the column. Vapors containing mostly 3O vapors comalnmg the Predommantly saturated saturated hydrocarbons with a very small amount ydroearbehs are condensed and cooled to a centage of phthalic anhydride is approximately A process according claim 2 in which the position of phthalic anhydride and saturated hytaming naphthaiehe as the Predominantly droearbone matic hydrocarbon constituent.

The portion of the liquid from the accumulator A process h i to claim 1 in which the 6 flow back as reflu through pipe 1 into the hydrocarbon mixtureisa petroleum product concolumn 2, entering at the point 8 at the top of the aihihg naphthalene as pr dominantly arosolvent-stripping section The rest of the liquid matic hydrocarbon eohstituehtg passes frem 5 through pipe '0 to the cooler rocess according to claim 1 in which the below the melting point of phthalic anhydride; admixture with miten Phthaiie anhydride is for example, to approximately C and the removed and the two constituents are separated latter crystallized out, the slurry of crystals passby instillationing through the pipe l2 into a centrifuge l3, A process according claim 5 which the where the liquid peramns are discharged to mixture is apetroleum product contain ng naphstorage through the pipe 25, and the solvent thaiene as h Predominantly aromatic hydrocrystals are removed as a solid cake. The loss of carbon constituentphthalic anhydride is very slight, as it is soluble A Process e i t0 ciaim i in which the in the paramns only to about 01 percent. hydrocarbon nnxture is a. petroleum product con- For most purposes the minute amount of taming behzehephthalic anhydride dissolved in the saturated hy- A Process eeeei'dihg t0 claim 1 in which the drocarbons is unobjectionable. If, however, very hydrocarbon mixture comprises benzene and pure hydrocarbons are required the last traces oi ph ahc anhydr de may be removed conven 9. A process according to Claim 1 Whlch the tional means, such as a wash with aqueous caustic hydhocarboh i' contains tetrahn as a P alkali.

The liquid from the bottom of the still, which 4 Process aecording to claim 1 in which a solut on of aromatics and anhydrjd the mixture Contalns dodecane as the predomi passes through the pipe l4 and is introduced into nanny saturated eompohehtthe middle of the solvent recovery still I5, pro- HAL B. H. COOPER. vided with a reboiler l6. As the aromatics are EUGENE C. MEDCALF. more volatile than phthalic anhydride, the latter passes out through the bottom of the still and References Cited in the me this Patent is recirculated through the pipe I 1 to the column U D STATES PATENTS additional make-up phthalic anhydride being Number Name Date introduced through the pipe I8. Vapors 01' 2 168 691 Voorhees Aug 8 1939 aromatics pass out of the top of the column 2:215915 Cope 1940 through pipe I9 to condenser 20, where the con- 2 37o530 Gage 1945 densed liquid flows down through pipe 2| into a 

1. A PROCESS OF SEPARATING PREDOMINANTLY AROMATIC HYDROCARBONS FROM PREDOMINANTLY SATURATED HYDROCARBONS OF SIMILAR BOILING POINTS WHICH COMPRISES SUBJECTING A MIXTURE OF HYDROCARBONS HAVING AT LEAST HALF THEIR MOLECULAR WEIGHT IN BENZENOID RINGS AND HYDROCARBONS OF SIMILAR BOILING POINT HAVING LESS THAN ONE DOUBLE BOND PER SIX CARBON ATOMS, THE MIXTURE HAVING A BOILING POINT BELOW THAT OF PHTHALIC ANHYDRIDE TO DISTILLATION UNDER PARTIAL REFLUX COUNTER-CURRENT TO A STREAM OF MOLTEN PHTHALIC ANHYDRIDE WHEREBY THE VAPOR PRESSURE OF THE PREDOMINATLY AROMATIC CONSTITUENTS OF THE MIXTURE IS DECREASED AND THE VAPOR PRESSURE OF THE PREDOMINANTLY SATURATED COMPONENT IS INCREASED, THE PREDOMINANTLY SATURATED HYDROCARBONS BEING OBTAINED AS AN OVERHEAD AND A SOLUTION OF PHTHALIC ANHYDRIDE AND THE PREDOMINANTLY AROMATIC HYDROCARBONS BEING OBTAINED FROM THE STILL IN LIQUID FORM. 